trans-Tricyclo<7.5.0.0^2,8>tetradeca-7,9-diene

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: trans-Tricyclo<7.5.0.0^2,8>tetradeca-7,9-diene
• 英文别名: trans-tricyclo[7.5.0.02,8]tetradeca-7,9-diene；rac.-Tricyclo<7.5.0.0^2.8>tetradecadien-(2,14)；Tricyclo<7.5.0.0^2,8>tetradeca-2,11-dien；(8S,9S)-tricyclo[7.5.0.02,8]tetradeca-1(14),2-diene
• 化学式: C₁₄H₂₀
• 分子量: 188.313
• InChiKey: IHHLJMYHJSFRHI-OCCSQVGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  trans-Tricyclo<7.5.0.0^2,8>tetradeca-7,9-diene 生成 cis-Tricyclo<7.5.0.0^2,8>tetradeca-7,9-diene
  参考文献：
  名称：

  Rearrangements of 1-cyclohexenylmethylenes and their relevance to the mechanism of the phenylcarbene rearrangement

  摘要：

  Gas-phase pyrolysis of 1-cyclohexenyldiazomethane (17) and (2-methyl-1-cyclohexenyl)diazomethane (36) leads to the generation of cyclohexenylmethylenes, 13 and 27, respectively, whose intramolecular rearrangement mechanisms can be inferred from the stable end products. These substituted vinylmethylenes undergo intramolecular pi-addition, but apparently do not participate in an all-carbon Wolff rearrangement. The relevance of these results to the mechanism of the phenylcarbene rearrangement is discussed, and it is suggested that a pi-route with a bicycloheptatriene-like transition state may operate. An attempt to generate 1,3-cyclohexadienylmethylene is described.

  DOI：

  10.1021/jo00017a021
• 作为产物：
  描述：

  双环[4.1.0]庚烷-7-甲酰氯 反应 1.5h， 以25%的产率得到trans-Tricyclo<7.5.0.0^2,8>tetradeca-7,9-diene
  参考文献：
  名称：

  Rearrangements of 1-cyclohexenylmethylenes and their relevance to the mechanism of the phenylcarbene rearrangement

  摘要：

  Gas-phase pyrolysis of 1-cyclohexenyldiazomethane (17) and (2-methyl-1-cyclohexenyl)diazomethane (36) leads to the generation of cyclohexenylmethylenes, 13 and 27, respectively, whose intramolecular rearrangement mechanisms can be inferred from the stable end products. These substituted vinylmethylenes undergo intramolecular pi-addition, but apparently do not participate in an all-carbon Wolff rearrangement. The relevance of these results to the mechanism of the phenylcarbene rearrangement is discussed, and it is suggested that a pi-route with a bicycloheptatriene-like transition state may operate. An attempt to generate 1,3-cyclohexadienylmethylene is described.

  DOI：

  10.1021/jo00017a021

文献信息

• A Mild Method for the Generation and Interception of 1,2-Cycloheptadienes with 1,3-Dipoles
  作者：Yaseen A. Almehmadi、F. G. West

  DOI：10.1021/acs.orglett.0c02172

  日期：2020.8.7

  Seven-membered cyclic allenes are mostly known for their propensity to undergo rapid dimerization, and relatively little has been reported regarding their cycloaddition reactivity with 1,3-dienes or 1,3-dipoles. This work describes the trapping of 1-acetoxy-1,2-cycloheptadiene and its unsubstituted counterpart, generated via desilylative elimination, with a range of 1,3-dipolar trapping partners, affording

  1,2-环庚二烯是一种应变的，瞬态物质，已未被充分利用为合成构件。七元环状亚丙基最因其易于快速二聚而闻名，关于它们与1,3-二烯或1,3-偶极的环加成反应性的报道相对较少。这项工作描述了通过一系列的1,3-偶极捕获伙伴，通过脱甲硅基消除生成的1-乙酰氧基-1,2-环庚二烯及其未取代的对应物，从而提供了具有高区域选择性和非对映选择性的复杂多环产物。
• Relative reactivities of bicyclo[3.2.1]octa-2,3-diene and 1,2-cycloheptadiene with conjugated dienes and styrene
  作者：A.T. Bottini、L.L. Hilton

  DOI：10.1016/0040-4020(75)80187-6

  日期：1975.1

  undergo cycloaddition reactions with 2,3-dimethylbutadiene, styrene, and 1,3-cyclopentadiene. 2, but not 3, was also found to undergo a (2 + 2) cycloaddition reaction with cis-pentadiene. The relative reactivities of 2 and 3 with cis-pentadiene, 2,3-dimethylbutadiene, styrene, and 1,3-cyclopentadiene at 60° in THF were found to be: 0·18, —; 1·0, 1·0; 0·60, 7·5; and 4·0, 150.

  发现通过用镁处理相应的二氯化物4和5生成的双环[3.2.1]辛基-2,3-二烯（2）和1,2-环庚二烯（3）与2,3-发生环加成反应。二甲基丁二烯，苯乙烯和1,3-环戊二烯。还发现2，但不是3，与顺式-戊二烯进行（2 + 2）环加成反应。发现2和3与顺式-戊二烯，2,3-二甲基丁二烯，苯乙烯和1,3-环戊二烯在60°的THF中的相对反应性为：0·18，-；1·0、1·0；0·60、7·5；和4·0、150。
• Reactions of 1-halocycloheptenes with potassium t-Butoxide and with sodium pyrrolidide
  作者：A.T. Bottini、K.A. Frost、B.R. Anderson、V. Dev

  DOI：10.1016/0040-4020(73)80133-4

  日期：1973.1

  Reactions of 1-halocycloheptenes with KO-t-Bu in DMSO and THF were studied. The principal products obtained could be accounted for on the basis of two competing dehydrohalogenation mechanisms. These are: dehydrohalogenation across the C1-C2 bond to give cycloheptyne; and dehydrohalogenation across the C1-C7 bond to give 1,2-cycloheptadiene. One or both of these intermediates react with KO-t-Bu to give

  研究了1-卤代环庚烯与KO-t-Bu在DMSO和THF中的反应。可以根据两种竞争的脱氢卤化机理解释所获得的主要产物。它们是：穿过C 1 -C 2键的脱卤化氢，得到环庚炔；并通过C 1 -C 7键脱卤化氢，得到1，2-环庚二烯。这些中间体中的一种或两种与KO-t-Bu反应以低收率得到1-t-丁氧基环庚烯。来自两种溶剂中的三个1-卤代环庚烯的主要产物是三环[7.5.0.0 2 8]十四烷基-2,14-二烯（4），即1,2-环庚二烯的二聚体。也形成有5，的2（8），14-二烯异构体4，推测是通过1,2-环庚二烯和cycloheptyne，和环加成6，的2,13二烯异构体4，通过重排4由KO叔卜实现。
• Criegee,R.; Reinhardt,H.G., Chemische Berichte, 1968, vol. 101, p. 102 - 112
  作者：Criegee,R.、Reinhardt,H.G.

  DOI：——

  日期：——
• Rearrangements of 1-cyclohexenylmethylenes and their relevance to the mechanism of the phenylcarbene rearrangement
  作者：Paula C. Miller、Peter P. Gaspar

  DOI：10.1021/jo00017a021

  日期：1991.8

  Gas-phase pyrolysis of 1-cyclohexenyldiazomethane (17) and (2-methyl-1-cyclohexenyl)diazomethane (36) leads to the generation of cyclohexenylmethylenes, 13 and 27, respectively, whose intramolecular rearrangement mechanisms can be inferred from the stable end products. These substituted vinylmethylenes undergo intramolecular pi-addition, but apparently do not participate in an all-carbon Wolff rearrangement. The relevance of these results to the mechanism of the phenylcarbene rearrangement is discussed, and it is suggested that a pi-route with a bicycloheptatriene-like transition state may operate. An attempt to generate 1,3-cyclohexadienylmethylene is described.